EP3825296B1 - Verfahren zur wärmebehandlung von mit schlamm infiltriertem faservorkörper - Google Patents

Verfahren zur wärmebehandlung von mit schlamm infiltriertem faservorkörper Download PDF

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Publication number
EP3825296B1
EP3825296B1 EP20206401.0A EP20206401A EP3825296B1 EP 3825296 B1 EP3825296 B1 EP 3825296B1 EP 20206401 A EP20206401 A EP 20206401A EP 3825296 B1 EP3825296 B1 EP 3825296B1
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Prior art keywords
fiber preform
preform
ceramic slurry
fluid bath
fiber
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EP20206401.0A
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English (en)
French (fr)
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EP3825296A1 (de
Inventor
Camila Bortoluzzi
Sungbo Shim
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Rolls Royce High Temperature Composites Inc
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Rolls Royce High Temperature Composites Inc
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5208—Fibers
    • C04B2235/5264—Fibers characterised by the diameter of the fibers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/614—Gas infiltration of green bodies or pre-forms
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/616—Liquid infiltration of green bodies or pre-forms
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density

Definitions

  • This disclosure relates generally to a method of forming ceramic matrix composite (CMC) articles. More specifically, this disclosure relates to a slurry infiltration heat treatment or transfer method used in the formation of the CMC articles.
  • CMC ceramic matrix composite
  • Ceramic matrix composite (CMC) are commonly used in a variety of structural applications due to their thermal resistance, high temperature strength, and chemical stability.
  • CMC ceramic matrix composite
  • a plurality of ceramic fibers are initially formed into a desired shape, i.e., into a preform, which may be subsequently rigidized with one or more ceramic phases.
  • the remaining porosity in the preform is then infiltrated with a ceramic slurry and bonded with a molten alloy.
  • a silicon carbide (SiC:SiC) matrix composite may be made by infiltrating a silicon carbide slurry into a porous SiC fiber preform followed by drying and the subsequent introduction of molten silicon or a silicon (Si) containing alloy into any porosity that remains in the slurry infiltrated preform through the use of capillary forces in order to densify the structure and form the CMC article.
  • the present disclosure is directed to a method in which the infiltration of the slurry includes an effective heat transfer mechanism.
  • the resulting green body of the present disclosure is more uniformly infiltrated with the ceramic slurry, which can maximize the efficiency of subsequent molten alloy infiltration steps and reduce the overall residual porosity within the finished article.
  • Chinese patent CN 103922779 B discloses a boundary phase-containing three-dimensional aluminum oxide fiber fabric-reinforced aluminosilicate ceramic and a preparation method thereof.
  • aluminosilicate is used as a matrix and a three-dimensional aluminum oxide fiber fabric is used as a reinforcing body, and a boron nitride boundary phase is formed between the matrix and the reinforcing body, wherein the boundary phase is prepared in a way of preparing a boron nitride coating on the surface of the fiber fabric.
  • United States patent US 5051226 discloses a method for curing fiber-reinforced resin matrix composite materials. The method involves providing a form and positioning uncured composite material on the form substantially into a desired shape. The composite material is then cured by providing a fluid bath heated to a predetermined temperature, and heating the composite material by immersing the positioned composite material on the form into the fluid bath for a predetermined time. The predetermined time is sufficient to allow the composite material to become cured and to heat the composite material at a rate sufficient to provide resin flow prior to hardening. Compressive pressure is provided on the composite material while it is immersed in the fluid bath.
  • United States patent application US 2016/009602 A1 discloses a method for reducing the thermal expansion/shrinkage behavior between fiber reinforced plies and monolithic matrix plies, and reducing the macroscopic defects that occur during process of making a ceramic matrix composite article.
  • the present invention provides a method of forming a green body for use in making a ceramic matrix composite (CMC) article, and a method of producing a ceramic matrix composite (CMC) article, as set out in the appended claims.
  • the present disclosure provides method of forming a green body for use in making a ceramic matrix composite (CMC) article; the method comprising: placing the fiber preform inside a pliable container having an internal volume and an external surface; infiltrating a ceramic slurry into a fiber preform to form a wet infiltrated preform; creating a pressure differential between the internal volume and the external surface of the pliable container, such that the ceramic slurry remains within the fiber preform; placing the pliable container and wet infiltrated preform into a fluid bath at ambient temperature; heating the fluid bath to a predetermined hold temperature; maintaining the fluid bath at the hold temperature for a predetermined time period, wherein the heat from the fluid bath is transferred to the wet infiltrated preform by convection, conduction, or a combination thereof, such that the wet infiltrated preform is transformed into the green body; removing the pliable container from the fluid bath; and removing the green body from the pliable container.
  • CMC ceramic matrix composite
  • the present disclosure provides a method of producing a ceramic matrix composite (CMC) article, the method comprising steps of: forming a fiber preform; optionally, rigidizing the fiber preform with a fiber interphase coating; transforming the fiber preform into a green body by the method of the first aspect; optionally, conducting one or more secondary operations on the green body; and infiltrating the green body with a molten silicon or silicon alloy to form the CMC article.
  • CMC ceramic matrix composite
  • the present disclosure provides a method of producing a melt infiltrated ceramic matrix composite (CMC) article, including, without limitation, silicon carbide matrix (SiC:SiC) composite articles.
  • This method generally comprises the steps of: forming a ceramic fiber preform; optionally, rigidizing the ceramic fiber preform with a fiber interphase coating via a Chemical Vapor Infiltration (CVI) process, infiltrating a ceramic slurry into the porous body or preform, optionally, conducting one or more secondary operations, and finally, melt infiltrating the preform with molten silicon or a silicon alloy to form the CMC article.
  • CVI Chemical Vapor Infiltration
  • CMCs ceramic matrix composites
  • the terms “at least one” and “one or more of” an element are used interchangeably and may have the same meaning. These terms, which refer to the inclusion of a single element or a plurality of the elements, may also be represented by the suffix "(s)"at the end of the element. For example, “at least one source”, “one or more sources”, and “source(s)” may be used interchangeably and are intended to have the same meaning.
  • the term "temperature control” describes controlling a temperature with minimal variation, such as ⁇ 5°C; alternatively, ⁇ 3°C; alternatively, ⁇ 1°C; alternatively, ⁇ 0.5°C.
  • this control over the variation in temperature may also be expressed as a percentage of the measured temperature. For example, as the measured temperature is controlled to be within ⁇ 10%; alternatively, ⁇ 5%; alternatively, ⁇ 3%; alternatively, ⁇ 1 %.
  • a concentration ranging from 40% by volume to 60% by volume includes concentrations of 40% by volume, 60% by volume, and all concentrations there between (e.g., 40.1%, 41%, 45%, 50%, 52.5%, 55%, 59%, etc.).
  • a method 1 of producing a ceramic matrix composite (CMC) article comprises the steps of: forming 10 a fiber preform; optionally, rigidizing 20 the fiber preform with a fiber interphase coating; transforming 30 the fiber preform into a green body; optionally, conducting 40 one or more secondary operations on the green body; and infiltrating 50 the green body with a molten silicon or silicon alloy to form the CMC article.
  • the step of transforming 30 the fiber preform into a green body is further subdivided into multiple steps 31-38 that are involved in performing such transformation.
  • the method of transforming or forming 30 the fiber preform into a green body comprises the steps of: placing 31 the fiber preform inside a pliable container having an internal volume and an external surface; infiltrating 32 a ceramic slurry into the fiber preform to form a wet infiltrated preform; creating 33 a pressure differential between the internal volume and the external surface of the pliable container, such that the ceramic slurry remains within the rigidized fiber preform; placing 34 the pliable container and wet infiltrated preform into a fluid bath at ambient temperature; heating 35 the fluid bath to a predetermined hold temperature; maintaining 36 the fluid bath at the hold temperature for a predetermined time period, wherein the heat from the fluid bath is transferred to the wet infiltrated preform by conduction, convection, or a combination thereof, such that the wet infiltrated preform is transformed into the green body; removing 37 the pliable container from the fluid bath; and removing 38 the green body from the pliable container.
  • a ceramic matrix composite (CMC) article is generally made from a lay-up of a plurality of continuous ceramic fibers, formed to a desired shape.
  • the lay-up is generally known as a ceramic fiber preform, fiber preform, or preform.
  • the fiber preform which may be partially rigid or non-rigid, may be constructed in any number of different configurations.
  • the preform may be made of filament windings, braiding, and/or knotting of fibers, and may include two-dimensional and three-dimensional fabrics, unidirectional fabrics, and/or nonwoven textiles.
  • the fibers used in the preform may comprise any number of different materials capable of withstanding the high processing temperatures used in preparing and operating CMC articles, such as, but not limited to, carbon fibers, ceramic fibers (e.g., silicon carbide, alumina, mullite, zirconia, or silicon nitride), which can be crystalline or amorphous.
  • the ceramic fibers may be suitably coated by various methods.
  • the fiber preform comprises fibers that include one or more of silicon carbide (SiC), silicon nitride (Si 3 N 4 ), or a mixture or combination thereof. Each of the fibers is individually selected and may be of the same or different composition and/or diameter.
  • the fibers are the same in at least one of said composition and/or diameter.
  • the ceramic fiber filaments may have a diameter that is between about 1 micrometer ( ⁇ m) to about 50 ⁇ m; alternatively, about 5 ⁇ m to about 30 ⁇ m; alternatively, about 10 ⁇ m to about 20 ⁇ m.
  • the ceramic fibers in the preform may be treated or rigidized by applying a single fiber interphase coating or a plurality of such coatings thereto.
  • the general purpose of the interphase coating(s) is to facilitate and/or enhance compatibility between the ceramic fibers and the ceramic slurry and/or the molten silicon or silicon alloy that is subsequently added in order to densify the preform and form the ceramic matrix composite.
  • the rigidizing of the fiber preform may also enhance the toughness (e.g., crack reduction) exhibited by the final CMC article, as well as reduce or prevent reaction between the ceramic fibers and the molten alloy.
  • the interphase coating(s) may be applied to the fiber preform using any method known to one skilled in the art, including but not limited to chemical vapor infiltration (CVI) or chemical vapor deposition (CVD) processes; alternatively, by a CVI process.
  • CVI chemical vapor infiltration
  • CVD chemical vapor deposition
  • interphase coatings include, without limitation, carbon, aluminum nitride, boron nitride, silicon nitride, silicon carbide, boron carbide, metal borides, transition metal silicides, transition metal oxides, transition metal silicates, rare earth metal silicates, and mixtures or combinations thereof.
  • the fiber interphase coating comprises silicon carbide (SiC), silicon nitride (Si 3 N 4 ), or a mixture or combination thereof.
  • the fiber interphase coating(s) may have a thickness that is in the range of about 0.01 micrometers ( ⁇ m) to about 20 micrometers ( ⁇ m); alternatively between about 0.05 ⁇ m to 15 ⁇ m; alternatively from about 0.1 ⁇ m to about 10 ⁇ m; alternatively, from about 0.5 ⁇ m to about 5 ⁇ m.
  • the fiber preform may be transformed 30 into a green body by the infiltration of a ceramic slurry into the preform and heating the ceramic slurry in the preform.
  • This ceramic slurry comprises, consists essentially of, or consists of a plurality of solid particulate fillers, one or more reactive additives, a solvent, and optionally, one or more dispersants, binders, and/or gelation polymers.
  • the ceramic slurry infiltrated into the porous fiber preform comprises a solid loading in the range of about 5 vol. % to about 80 vol. %; alternatively in the range of about 10 vol. % to about 70 vol. %; alternatively, in the range of about 15 vol. % to about 65 vol. %; alternatively, in the range of about 20 vol. % to about 60 vol. %, relative to the overall volume of the ceramic slurry.
  • the solid particulate fillers flow into the pores and interstices that exist between the ceramic fibers.
  • the infiltration 32 of the ceramic slurry may be accomplished in a single step or may comprise multiple infiltration steps in order to ensure that the fiber preform is fully impregnated with the solid particulate fillers.
  • Each additional infiltration step may be performed using a ceramic slurry composition that is either the same as or different form the composition used in the first impregnation step.
  • the solid particulate fillers in the ceramic slurry may comprise, without limitation aluminum nitride, aluminum diboride, boron carbide, alumina, mullite, zirconia, carbon, silicon carbide, silicon nitride, transition metal nitrides, transition metal borides, rare earth oxides, and mixtures and combinations thereof.
  • the solid particulate fillers comprise silicon carbide (SiC), silicon nitride (Si 3 N 4 ), or a mixture or combination thereof.
  • the solid particulate fillers may comprise one or more regular or irregular shapes including, without limitation, spheres and rods.
  • the size of the solid particulate fillers may vary, but generally, exhibit a diameter, i.e., the length of major dimension, that is less than about 50 micrometers; alternatively in the range of about 100 nanometers (nm) up to about 50 micrometers ( ⁇ m); alternatively, greater than 200 nm; alternatively, between about 300 nm and about 25 ⁇ m.
  • the solid particulate fillers are typically present in various sizes and give rise to a particle size distribution that can be characterized by a mean average particle size or diameter. These solid particulate fillers may result in a mono-, bi-, or multi-modal distribution being observed upon the measurement of a particle size distribution for the ceramic slurry using any conventional technique, such as sieving, microscopy, Coulter counting, dynamic light scattering, or particle imaging analysis, to name a few.
  • the one or more reactive additives included in the composition of the ceramic slurry may comprise, without limitation, at least one of graphite, diamond, carbon black, molybdenum (Mo), and tungsten (W).
  • the solvent present in the ceramic slurry may be any solvent known for use in such materials used to infiltrate fiber preforms during the formation a ceramic matrix composite (CMC) article.
  • solvents include, but are not limited to, polyvinylpyrrolidone, isopropanol, polyvinyl alcohol, water, and mixtures thereof.
  • the one or more dispersants, optionally included in the composition of the ceramic slurry may comprise, but not be limited to, an anionic, cationic, or nonionic surfactant, including for example, polyethylene glycol (PEG).
  • the optional binders included in the composition of the ceramic slurry may comprise, without limitation, polyethyleneimine (PEI).
  • PEI polyethyleneimine
  • the composition of any optional gelation polymers may include, but not be limited to, carboxymethyl cellulose.
  • the reactive additives and the optional dispersants and/or binders present in the ceramic slurry are not the same as the pre-gelation materials conventionally incorporated into a ceramic slurry, including those described in U.S. Patent No. 9630885 .
  • pre-gelation materials include polysaccharides, such as methyl cellulose, carboxymethyl cellulose, hydroxypropyl methyl cellulose, gellan gum, agarose, carrageenan, and mixtures and combinations thereof.
  • the ceramic slurry of the present disclosure does not need or require the presence of such pre-gelation materials.
  • a ceramic slurry that incorporates such pre-gelation materials may be utilized and receive the benefits associated with the method described herein.
  • the ceramic slurry of the present disclosure does not include any such pre-gelation materials.
  • Pre-gelation materials are conventionally used to enhance the uniformity of infiltration of the slurry particulate into the interstices (e.g., pores) of the preform, and ensure that the particles in the slurry remain in said interstices during subsequent processing steps.
  • the pre-gelation material becomes at least partially gelled after the slurry infiltrates into the interstices in the fiber preform, thereby providing a network capable of retaining the slurry particulates in the interstices during subsequent processing steps.
  • the establishment of this network is necessary because the application of heat to dry the ceramic slurry and form a green body conventionally is accomplished via an inefficient free convection heat transfer mechanism.
  • a gas e.g., air
  • one or more heat transfer methods are utilized, such that heat reaches the wet infiltrated preform more quickly. More specifically, heat is transferred by the movement of the fluid to the infiltrated fiber preform via convection. In this process, the fluid is heated, such that hot areas of the fluid flow and mix with the cool areas of the fluid in the bath.
  • convection heating represents an effective way of moving a hot fluid or a cold fluid from one area to another area in the bath.
  • Thermal energy in the present disclosure may also be transferred via conduction from one substance to another substance when the substances are in direct contact with each other and/or movement of the fluid is no longer actively occurring.
  • heat travels through a material as one molecule transfers energy to neighboring molecules.
  • CMC ceramic matrix composite
  • the temperature difference between the fluid bath and the ceramic slurry in the wet infiltrated preform is less than 5°C; alternatively, less than 3°C; alternatively, between about 0.5°C and about 4°C.
  • the fluid used in the heated bath is not necessarily limited. This fluid may be, without limitation, water; an alcohol, such as methanol, ethanol, or propanol; an oil, such as silicone oil or mineral oil; a glycol, such as ethylene glycol or propylene glycol; glycerol; perfluorocarbon fluid; or any desirable mixture or combination thereof.
  • the heat generated by the fluid bath is equilibrated with the surface of the pliable container by convection arising from the movement of the fluid in the bath and subsequently transferred via a conduction in the absence of fluid movement to the ceramic slurry that is infiltrated into fiber preform.
  • the use of such convection and/or conduction mechanisms allows the heat to be delivered into the fiber preform much quicker than through a free convection mechanism as used in a conventional process.
  • the use of the heat transfer method of the present disclosure reduces the overall processing time by allowing the next batch of fiber preforms to be processed into ceramic matrix composite (CMC) articles from minutes to hours earlier; alternatively, at least 3 hours earlier.
  • CMC ceramic matrix composite
  • the fluid bath is heated from ambient temperature (about 20°C) to a predetermined hold temperature, which is in the range from about 25°C to about 80°C; alternatively, from about 30°C to about 80°C; alternatively, from about 35°C to about 75°C.
  • the heating of the fluid bath is performed at a rate that ranges from about 0.1°C/min to about 3.0°C/min; alternatively, from about 0.3°C/min to about 2.5°C/min; alternatively, from about 0.5°C/min to about 2.0°C/min, such that the predetermined hold temperature is reached in less than 2 hours.
  • the hold temperature is reached in less than 90 minutes; less than 60 minutes; or in about 50 minutes.
  • Temperature control is conducted, such that the hold temperature is maintained for a predetermined time period that ranges from about 5 minutes to about 24 hours; alternatively, from about 1 hour to about 15 hours; alternatively, from about 3 hours to about 12 hours; alternatively, greater than 3 hours and less than 8 hours.
  • the fluid bath may be a heated bath circulator in which the fluid is circulated in order to distribute the heat throughout the bath efficiently and homogenously. The use of such a heated bath circulator assists in ensuring that heat transfer from the fluid bath to the ceramic slurry in the wet infiltrated preform is uniformly distributed.
  • the pliable container in which the fiber preform prior to being infiltrated with the ceramic slurry is placed may include, without limitation, a plastic bag or a pouch formed from a polymeric sheet or film.
  • the pliable container is typically sealed on three sides with the fourth side being reversibly sealable after the wet, infiltrated fiber preform is placed therein.
  • the plastic bag or pouch effectively encapsulates the infiltrated fiber preform and provides a barrier between the preform and the fluid in the fluid bath.
  • the composition of the pliable container may be any polymeric material that can withstand the application of a pressure differential and the temperature at which the fluid bath is heated.
  • a pressure differential may be created between the internal volume and external surface of the pliable container by any method known in the art, including but not limited to creating a vacuum. This pressure differential may be created prior to infiltration and maintained during infiltration of the ceramic slurry into the fiber preform.
  • the green body may be subjected to 40 one or more secondary operations when necessary or desirable.
  • these secondary operations include, without limitation, the removal of excess ceramic slurry, defects, or other surface imperfections from the green body, as well as drying the green body in order to remove fluid or other residual solvents that may remain within the green body.
  • the removal of the imperfections or defects may be accomplished by any means known to one skilled in the art, including but not limited to grinding, sanding, brushing, or polishing with or without the an abrasive medium.
  • the drying of the green body may be accomplished by any suitable manner, including without limitation, drying at ambient temperature under vacuum at about 1 Torr or at ambient pressure along with exposure to a predetermined temperature that ranges from ambient or room temperature (about 20°C) up to 400°C; alternatively, the predetermined temperature is greater than 100°C; alternatively from about 150°C to about 300°C.
  • the ramp rate used to increase the temperature from ambient temperature up to the predetermined temperature may be on the order of less than 2°C per minute; alternatively about 1.5°C per minute; alternatively between about 1°C/minute to about 2°C/minute.
  • CMC ceramic matrix composite
  • a molten metal or metal alloy is infiltrated 50 into any porosity that remains or is still present in the fiber preform.
  • a molten metal or metal alloy is infiltrated 50 into the green body. This molten metal or metal alloy occupies any remaining interstices that may be present between the solid particulate fillers and ceramic fibers until the green body is fully densified to less than about 7% porosity; alternatively, 5% porosity; alternatively, less than about 3% porosity; alternatively, between 0% and about 1% porosity in the finished CMC article.
  • metal or alloy is intended to refer to a matrix infiltrant, which may comprise any number of materials such as, but not limited to, polymers, metals, and ceramics.
  • metals that may be used to infiltrate the fiber preform may comprise, without limitation, aluminum, silicon, nickel, titanium, or mixtures and alloys thereof.
  • ceramics that may be used to infiltrate the fiber preform may include, without limitation, silicon carbide, silicon nitride, alumina, mullite, zirconia, and combinations thereof.
  • the metal or metal alloy infiltrant is silicon, silicon carbide, silicon nitride, or a combination thereof (e.g., silicon/silicon carbide, etc.).
  • the metal or metal alloy particles may be combined with other additives or process aids.
  • the infiltration of the metal or metal alloy may be accomplished at a temperature of at least 1,000°C; alternatively, about 1,200°C to about 1,700°C; alternatively, between about 1,350°C and about 1,550°C.
  • the duration of the infiltration may range between about 5 minutes to 5 hours; alternatively, from 15 minutes to 4 hours; alternatively, from about 20 minutes to about 2 hours.
  • the infiltration of the molten silicon or silicon alloy may optionally be carried out under vacuum or in an inert environment under atmospheric pressure in order to minimize evaporative losses.
  • the CMC article may optionally be machined to form a suitable finished component or article.
  • a method of forming a green body for use in making a ceramic matrix composite (CMC) article is provided.
  • this method 30 is similar to or substantially the same as the method described above with respect to steps 31-38.
  • This heat transfer system 100 generally comprises an eighteen (18) quart clear container 105, a thermal immersion circulator 110, a data acquisition (DAQ) system 115, and one or more thermocouples 120.
  • DAQ data acquisition
  • the steps in the method of forming a CMC article as described above and in Figure 1 were conducted with the fiber preform being placed into a pliable container 210, the fiber preform being infiltrated with a ceramic slurry to form an infiltrated fiber preform 200 under vacuum and then heated through the use of a convection and conduction mechanisms (i.e., transfer of heat from the fluid bath into the slurry infiltrated fiber preform) until fully cured and then subsequently subjected to melt infiltration of silicon or a silicon alloy.
  • a convection and conduction mechanisms i.e., transfer of heat from the fluid bath into the slurry infiltrated fiber preform
  • the CMC articles processed using the prototype heat transfer system 100 were subjected to inspection and mechanical tests. The results of this inspection and mechanical testing has demonstrated that the processed CMC articles exhibit or display at least equivalent behavior to identical CMC articles processed using a conventional heat transfer process.
  • the production heat transfer system 100A includes and industrial fluid bath 105A equipped with a circulation unit 110A and connected to a data acquisition (DAQ) system and one or more thermocouples (not shown).
  • DAQ data acquisition
  • the steps in the method of forming a CMC article as described above and in Figure 1 were conducted with the fiber preform being placed into a pliable container 210A, the fiber preform being infiltrated with a ceramic slurry to form an infiltrated fiber preform 200A under vacuum and then heated through the use of conduction and convection mechanisms (i.e., transfer of heat from the production fluid bath into the slurry infiltrated fiber preform) until fully cured and then subsequently subjected to melt infiltration of silicon or a silicon alloy.
  • conduction and convection mechanisms i.e., transfer of heat from the production fluid bath into the slurry infiltrated fiber preform
  • the CMC parts processed using the production heat transfer system 100A were subjected to inspection and mechanical tests. The results of this inspection and mechanical testing has demonstrated that the processed CMC articles exhibit or display at least equivalent behavior to identical CMC articles processed using a conventional heat transfer process.

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Claims (15)

  1. Verfahren zum Bilden eines Grünkörpers zur Verwendung beim Herstellen eines Gegenstands aus einem Keramikmatrix-Verbundwerkstoff (CMC); wobei das Verfahren umfasst:
    Platzieren eines Faservorformlings in einem biegsamen Behälter (210A), der ein Innenvolumen und eine Außenfläche aufweist;
    Infiltrieren (32) eines Keramikschlickers in einen Faservorformling, um einen nassinfiltrierten Vorformling zu bilden;
    Erzeugen (33) einer Druckdifferenz zwischen dem Innenvolumen und der Außenfläche des biegsamen Behälters, sodass der Keramikschlicker im Faservorformling verbleibt;
    Platzieren (34) des biegsamen Behälters und des nassinfiltrierten Vorformlings in ein Flüssigkeitsbad (105, 105A) bei Umgebungstemperatur;
    Erhitzen (35) des Flüssigkeitsbades auf eine vorbestimmte Haltetemperatur;
    Halten (36) des Flüssigkeitsbads auf der Haltetemperatur für einen vorbestimmten Zeitraum, wobei die Wärme vom Flüssigkeitsbad durch Konvektion, Leitung oder eine Kombination davon auf den nassinfiltrierten Vorformling übertragen wird, sodass der nassinfiltrierte Vorformling in den Grünkörper umgewandelt wird;
    Entfernen (37) des biegsamen Behälters aus dem Flüssigkeitsbad; und
    Entfernen (38) des Grünkörpers aus dem biegsamen Behälter.
  2. Verfahren nach Anspruch 1, wobei der Keramikschlicker aus einer Vielzahl fester teilchenförmiger Füllstoffe, einem oder mehreren reaktiven Zusatzstoffen, einem Lösungsmittel und optional einem oder mehreren Dispergiermitteln, Bindemitteln und/oder Gelierungspolymeren besteht;
    die festen teilchenförmigen Füllstoffe Siliziumkarbid (SiC), Siliziumnitrid (Si3N4) oder eine Mischung davon umfassen, die in einer Feststoffbeladung im Bereich von etwa 10 Vol.-% bis etwa 70 Vol.-%, bezogen auf das Gesamtvolumen des Keramikschlickers, vorliegen; und
    der eine oder die mehreren reaktiven Zusatzstoffe mindestens eines von Graphit, Diamant, Ruß, Molybdän (Mo) und Wolfram (W) beinhalten.
  3. Verfahren nach Anspruch 1 oder 2, wobei der Faservorformling Fasern umfasst, die eines oder mehrere von Siliziumkarbid (SiC), Siliziumnitrid (Si3N4) oder einer Mischung davon beinhalten; und
    der Faservorformling optional über einen Prozess der chemischen Dampfinfiltration (CVI) mit einer Faserzwischenphasenbeschichtung versteift (20) wird, die Siliziumkarbid (SiC), Siliziumnitrid (Si3N4) oder eine Mischung davon umfasst.
  4. Verfahren nach einem der vorhergehenden Ansprüche, wobei das Flüssigkeitsbad (105, 105A) ein beheizter Badzirkulator ist, sodass die Wärmeübertragung von dem Flüssigkeitsbad auf den Keramikschlicker im nassinfiltrierten Vorformling (200, 200A) gleichmäßig verteilt ist.
  5. Verfahren (1) zum Produzieren eines Gegenstands aus einem Keramikmatrix-Verbundwerkstoff (CMC), wobei das Verfahren die Schritte umfasst:
    Bilden (10) eines Faservorformlings;
    optional Versteifen (20) des Faservorformlings mit einer Faserzwischenphasenbeschichtung;
    Umwandeln (30) des Faservorformlings in einen Grünkörper durch das Verfahren nach einem der Ansprüche 1 bis 4;
    optional Durchführen (40) eines oder mehrerer sekundärer Vorgänge am Grünkörper; und
    Infiltrieren (50) des Grünkörpers mit geschmolzenem Silizium oder einer geschmolzenen Siliziumlegierung, um den CMC-Gegenstand zu bilden.
  6. Verfahren nach Anspruch 5, wobei der Keramikschlicker aus einer Vielzahl fester teilchenförmiger Füllstoffe, einem oder mehreren reaktiven Zusatzstoffen, einem Lösungsmittel und optional einem oder mehreren Dispergiermitteln, Bindemitteln und/oder Gelierungspolymeren besteht.
  7. Verfahren nach Anspruch 6, wobei die festen teilchenförmigen Füllstoffe Siliziumkarbid (SiC), Siliziumnitrid (Si3N4) oder eine Mischung davon umfassen.
  8. Verfahren nach Anspruch 6, wobei der eine oder die mehreren reaktiven Zusatzstoffe mindestens eines von Graphit, Diamant, Ruß, Molybdän (Mo) und Wolfram (W) beinhalten.
  9. Verfahren nach einem der Ansprüche 5 bis 8, wobei der in den Faservorformling (200, 200A) infiltrierte Keramikschlicker eine Feststoffbeladung im Bereich von 10 Vol.-% bis 70 Vol.- %, bezogen auf das Gesamtvolumen des Keramischlickers, umfasst.
  10. Verfahren nach einem der Ansprüche 5 bis 9, wobei das Versteifen (20) des Faservorformlings mit einer Faserzwischenphasenbeschichtung einen Prozess der chemischen Dampfinfiltration (CVI) verwendet.
  11. Verfahren nach einem der Ansprüche 5 bis 10, wobei die Faserzwischenphasenbeschichtung Siliziumkarbid (SiC), Siliziumnitrid (Si3N4) oder eine Mischung davon umfasst.
  12. Verfahren nach einem der Ansprüche 5 bis 11, wobei der Faservorformling Fasern umfasst, die eines oder mehrere von Siliziumkarbid (SiC), Siliziumnitrid (Si3N4) oder einer Mischung davon beinhalten.
  13. Verfahren nach einem der Ansprüche 5 bis 12, wobei das Erhitzen des Flüssigkeitsbades (105, 105A) ein Erhitzen mit einer Geschwindigkeit im Bereich von etwa 0,5 °C/min bis etwa 2 °C/min umfasst.
  14. Verfahren nach einem der Ansprüche 5 bis 13, wobei der Temperaturunterschied zwischen dem Flüssigkeitsbad (105, 105A) und dem Keramikschlicker im nassinfiltrierten Vorformling (200, 200A) weniger als 3°C beträgt.
  15. Verfahren nach einem der Ansprüche 5 bis 14, wobei das Flüssigkeitsbad (105, 105A) ein beheizter Badzirkulator ist, sodass die Wärmeübertragung von dem Flüssigkeitsbad auf den Keramikschlicker im nassinfiltrierten Vorformling (200, 200A) gleichmäßig verteilt ist.
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US20230159397A1 (en) * 2021-11-19 2023-05-25 Raytheon Technologies Corporation Ceramic matrix composite article and method of making the same
US11919088B1 (en) 2021-12-23 2024-03-05 Rolls-Royce High Temperature Composites Inc. Pressure assisted melt infiltration
US12000046B1 (en) 2021-12-29 2024-06-04 Rolls-Royce High Temperature Composites, Inc. Load assemblies for loading parts in a furnace
US12078417B1 (en) 2021-12-29 2024-09-03 Rolls-Royce High Temperature Composites, Inc. Load assemblies for loading parts in a furnace
US11932941B1 (en) 2021-12-29 2024-03-19 Rolls-Royce High Temperature Composites, Inc. Load assemblies for loading parts in a furnace
US11912628B1 (en) 2021-12-29 2024-02-27 Rolls-Royce High Temperature Composites, Inc. Slurry infiltration fixture

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US5051226A (en) 1989-09-18 1991-09-24 The Boeing Company Method of curing composite parts
US20160009602A1 (en) 2013-03-08 2016-01-14 General Electric Company Methods for reducing the process-induced shrinkage in a ceramic matrix composite, and articles made therefrom
US11351652B2 (en) * 2013-05-02 2022-06-07 Melior Innovations, Inc. Polysilocarb binders and coatings
CN103922779B (zh) 2014-04-10 2015-07-01 中国人民解放军国防科学技术大学 含界面相的三维氧化铝纤维织物增强铝硅酸盐陶瓷及其制备方法
EP3000797B1 (de) 2014-09-24 2019-11-27 Rolls-Royce Corporation Verfahren zur herstellung von artikeln aus keramischen matrix-verbundwerkstoffen mit gelierungsschritt
US20170059165A1 (en) * 2015-08-28 2017-03-02 Rolls-Royce High Temperature Composites Inc. Cmc cross-over tube
JP6630770B6 (ja) * 2017-04-19 2020-03-18 ロールス−ロイス ハイ テンペラチャー コンポジッツ，インコーポレーテッド 保護セラミックコーティングを有するセラミックス基複合材料（ｃｍｃ）の処理方法

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